Polar substituted polymers as detergents-viscosity index improvers



United States Patent US. Cl. 25232.7 17 Claims ABSTRACT OF THEDISCLOSURE Terpolymers having two different l-olefins of from 2 to 6carbon atoms and l-olefin of from 4 to 30 carbon atoms having at leastone basic nitrogen atom at least ,6 to the olefinic carbon atom or ahighly hindered basic nitrogen atom at least a to the olefinic carbonatom. The polymers have an intrinsic viscosity in the range of 0.2 to1.5 dl./g. The polymers find use in lubricating oils for viscosity indeximprovement, acid neutralization and detergency.

Cross references to related applications This application is acontinuation-in-part of applicatron Ser. No. 477,935, filed Aug. 6,1965, now abandoned.

Background of the invention Field of the invention.Numerous additivesare incorporated in lubricating oils used for internal combustionengines, not only to improve the lubrication by the oil, but also toprovide the stable dispersion of sludges and other deposit-formingmaterials in the oil. Desirably, detergents and dispersants should notonly be efiective under the hot conditions of the diesel engines, butalso under the much more variable conditions of the automobile engine.In the relatively low temperature gasoline engine operation encounteredin stop-and-go passenger car service, where fuel oxidation products area major source of deposits. the use of lubricating oil detergents isparticularly important.

Also, it is necessary that lubricating oils have a reasonable viscosityover a wide temperature range in order to provide proper lubrication. Toachieve this result, viscosity index improvers are added to thelubricating oil. These agents ordinarily do not significantly affect theoil at low temperatures, but enhance the viscosity at high temperatures.

In detergents, it is also desirable that some acid neutralization 'beprovided, since with sulfur containing fuels and lubricating oils,mineral acids are formed. These acidic materials are extremelycorrosive, and neutralization reduces the corrosion and wear resultingfrom the acids.

Description of the prior art.-In the last ten years, numerous patentshave been issued on ashless lubricating oil detergents. See, forexample, U.S. Patents Nos. 3,219,666, 3,200,076 and 3,275,554. For themost part, these compositions have been based on the oil solublepolypropenyl or polyisobutenyl hydrocarbon group.

Other patents have issued disclosing amine modified polymers for use inlubricating oils. See, for example, US. Patent Nos. 2,794,312,2,838,456, 3,092,563 and 3,125,462.

3,445,387 Patented May 20, 1969 Summary of the invention Terpolymers areprovided having two different aliphatic hydrocarbon 1olefins of from 2to 6 carbon atoms and one mono-substituted aliphatic hydrocarbonl-olefin of from 4 to 30 carbon atoms, wherein the monosubstituent hasat least one basic nitrogen at least 8 to the double bond, except whenthe nitrogen atom is highly hindered. The basic nitrogen atoms arebonded solely to hydrogen, carbon, nitrogen and silicon atoms.

The polymers have an intrinsic viscosity in the range of about 0.2 to1.5 dL/g. (as determined in Tetralin at C.).

When added to lubricating oils for use in internal combustion engines,the polymers provide detergency and dispersancy, viscosity indeximprovement and acid neutralization.

Description of the preferred embodiments The terpolymers of thisinvention have three olefins: two aliphatic hydrocarbon a-olefins offrom 2 to 6 carbon atoms; and a third mono-substituted aliphatichydrocarbon lZ-Olfifil'l of from 3 to 30 carbon atoms, themono-substituent having at least one basic nitrogen atom. The polymerswill have an intrinsic viscosity (as determined in Tetralin at 135 C.)in the range of about 0.2 to 1.5 dl./g., more usually in the range ofabout 0.4 to 1.2 dl./g. As estimated from the intrinsic viscositymeasurements, based on a graph in the following reference, Moraglio,Chem. e ind. (Milano), 41, 989 (1959), polymers will have a molecularweight in the range of about 10,000 to 120,000, more usually in therange of about 16,000 to 90,000.

The hydrocarbon a-olefins of from 2 to 6 carbon atoms include ethylene,propylene, butene-l, 4-methylpentene-1, hexene-l, etc. Preferred olefinsdo not have a branch nearer than one carbon atom removed from the vinylcarbon atom, e.g., CHFCHCHZCE. Particularly preferred is the combinationof ethylene and propylene.

The polymers will have from about 0.05 to 2 weight percent basicnitrogen, more usually from about 0.06 to 1 weight percent basicnitrogen. By basic nitrogen is intended which can be titrated withperchloric acid potentiometrically; usually the nitrogen will have asingle or higher order of bonding (double or triple) to hydrogen,carbon, nitrogen, or silicon, most usually hydrogen or carbon; and thecarbon, nitrogen or silicon to which the basic nitrogen is bonded willbe bonded only to carbon or hydrogen. Usually, the nitrogen will besingly bonded to carbon and/ or hydrogen.

The basic nitrogen atom will be at least one carbon removed from thebackbone of the polymer and then only when it is highly stericallyhindered. (By highly sterically hindered is intended at least one groupbonded to nitrogen having 3 carbon atoms bonded to the central atom (Cor Si) which is bonded to nitrogen.) Otherwise, the basic nitrogen willbe at least two carbons removed from the backbone of the polymer andpreferably at least three carbons removed from the backbone of thepolymer.

Generally, on the average there will be at least one amino substitutedolefin per polymer molecule and more usually greater than one and fewerthan ten. Most usually, on the average there will be more than one andfewer than five amino substituted olefins per polymer molecule. Inevaluating the average, the amounts of polymeric material, if any,having no amine substituent, will not be included in the average.However, to the degree such nonamine substituted (hydrocarbon) polymersare present in the examples, the percent nitrogen reported will bereduced.

The polymers will for the most part have the following formula:

(C'Hr-(EII) (GHQ-CH) (CIIz-CPI R 1 ii in XY I:

wherein R and R are ditierent and are either hydrogen or lower alkyl offrom 1 to 4 carbon atoms, usually of from 1 to 3 carbon atoms, i.e.,methyl, ethyl or propyl. When alkyl, R and R may be branched or straightchain, preferably straight chain, and not branched at the a-carbon,i.e., the carbon atom bonded to the vinyl carbon is methylene.

X is alkylene of from 1 to 10 carbon atoms, most usually from 2 to 6carbon atoms and Y is a basic nitrogen containing radical, generally offrom to 16 carbon atoms, more usually of from 2 to 12 carbon atoms. Ymay have up to 6 basic nitrogen atoms, but will generally only have fromabout 1 to basic nitrogen atoms, most usually as amino groups. Y mayalso have from 1 to 2 silicon atoms, the silicon generally bonded tonitrogen, and from 0 to 2 oxygen atoms.

I, m and n are the number percent of the individual monomers and add upto 100%. n as an average will generally be in the range of greater than0.05 to 5%, preferably in the range of about 0.1 to 3%, and particularlypreferred, 0.1 to 1%. I and m will generally each be in the range ofabout 25 to 75%, more usually in the range of about 30 to 70% and thesum of l+m will be in the range of about 95 to 99.95%, more usually inthe range of about 97 to 99.9%.

Since the polymers of this invention are lubricating oil additives, theymust be compatible with hydrocarbon lubricating oils over a widetemperature range. Also, the polymer must be compatible with a widevariety of oil additives. The subject polymer in order to be compatible,depending on the hydrocarbon olefin monomer combination, will have asindicated above at least 25 mol percent and, preferably, at least 30 molpercent of one monomer.

A preferred hydrocarbon monomer combination is ethylene and propylene.In this combination there should be less than about 70 mol percentethylene (respectively 30% propylene), usually 40-70 mol percentethylene and respectively 30-60 mol percent propylene. The preferredrange for the monomers is 4560 mol percent ethylene and respectively554O mol percent propylene.

The polymers are prepared with catalysts providing little, if any,stereoregularity. That is, the polymers will be amorphous-little or nocrystallinity. The polymers are random as to the hydrocarbon monomersand, also preferably as to the containing monomers. These polymers willnot create a haze with the common lubricating oils, e.g., Mid-Continent100-200 neutral oils at usual additive concentrations (1-10 weightpercent), even at low temerature, e.g., C. or below.

When referring to the various values, such as mol percent, it isintended that average values be understood. The mol percent should berelatively uniform over all the polymer molecules except at low nitrogencontent. With decreasing nitrogen content, a limit is reached whenhydrocarbon polymers-mo nitrogen containing monomer is incorporatedareobtained. The low nitrogen values do not reflect an increasing molecularWeight, but rather the presence of inert hydrocarbon polymers.

The hydrocarbon polymer affects the reported nitrogen and equivalentweight values which are determined from a nitrogen analysis on the totalproduct.

The basic nitrogen containing olefin which may be incorporated directlyor represents the monomer which may be introduced into the polymer by anindirect method, will have the following formula:

wherein X is an alkylene group of from 1 to 10 carbon atoms, moreusually of from 2 to 6 carbon atoms, and Y is a basic nitrogencontaining radical, usually bonded through a basic nitrogen to X. Y willordinarily have from 0 to 16 carbon atoms, more usually from 2 to 12carbon atoms, and most usually from 2 to 8 carbon atoms, will have from1 to 6 basic nitrogen atoms, more usually from 1 to 5 basic nitrogenatoms and may have from 0 to 2 silicon atoms.

Also, oxygen may be present, as hydroxyl or ethereal groups bonded tocarbon. Normally, from 1 to 2 oxygen atoms may be present. Except forthe heterocyclic amine groups, the carbon atoms for the most part willbe saturated aliphatic carbon atoms, although some aliphatic (olefinic)unsaturation may be present, with multiple bonding either to carbon ornitrogen; the carbon atoms may be present to form alkyl groups, alkenylgroups, or in combination with the nitrogen atoms, oxygen atoms orsilicon atoms, heterocyclic rings having from 5 to 6 annular members. Yis usually free of aromatic unsaturation, although heterocyclic aminesmay contain aromatic unsaturation.

The first class of substituents will be the simple mono amine and itsderivatives. The olefin having this monoamine substituent will for themost part have the following formula:

0 m=on wherein X is alkylene of from 1 to 10 carbon atoms, more usuallyfrom 2 to 6 carbon atoms, and preferably polymethylene of from 2 to 6carbon atoms, and T and "I" may be the same or different. T and "I maybe hydrogen, or hydrocarbon radicals of from 1 to 12 carbon atoms, moreusually of from 1 to 8 carbon atoms, hydroxy or alkoxy hydrocarbonradicals of from 2 to 10 carbon atoms, more usually of from 2 to 8carbon atoms, or trialkyl silyl radicals of from 3 to 12 carbon atoms,more usually of from 3 to 9 carbon atoms. For the most part, T and Twill be hydrogen or saturated aliphatic hydrocarbon radicals of from 1to 6 carbon atoms or saturated hydroxy or alkoxy aliphatic hydrocarbonradicals of from 2 to 6 carbon atoms.

Illustrative amino substituents are amino, methylamino, propylamino,dimethylamino, dihexylamino, hydroxyethylamino, di(hydroxyethyl)amino,methoxypropylamino, ditrimethylsilylamino, decylamino, etc.

A second group of amine substituted olefins are alkylene polyamines orpolyalkylene polyamines having two or more basic nitrogen atoms, moreusually from about 2 to 6 nitrogen atoms, and preferably from about 2 to5 basic nitrogen atoms. These olefins will for the most part have thefollowing formula:

wherein X is alkylene of from 2 to 10 carbon atoms, more usually of from2 to 6 carbon atoms, and preferably polymethylene of from 2 to 6 carbonatoms, Z is alkylene of from 2 to 6 carbon atoms, more usually of from 2to 3 carbon atoms, there being at least 2 carbon atoms between thenitrogen atoms, and p is an integer of from 1 to 5, more usually of from1 to 4.

Illustrative alkylene polyamines and polyalkylene polyamines areethylene diamine, diethylene triamine, triethylene, tetramine,tetraethylene pentamine, dipropylene triamine, hexamethylene diamine,tris(2-aminoethyl)amine, etc.

Equivalent to the alkylene polyamines are piperazines and aminoalkylenepiperazines which are provided for in following formula.

Another group of basic nitrogen containing substituted monoolefins havethe following formula:

wherein X is alkylene of from 2 to carbon atoms, more usually of from 2to 6 carbon atoms, and preferably polymethylene of from 2 to 6 carbonatoms; for the symbols in parentheses, N and C have their ordinarymeaning of nitrogen and carbon, respectively, A and D may be the same ordifferent and are nitrogen or oxygen, a, c and e are integers of from 0to 3, b and d are integers of from 0 to l, and the sum of a, b, c, d ande is in the range of 4 to 5. The bonds between the annular members maybe single or alternating double, there being from 0 to 3 double bonds inthe ring, and the valences of the annular members being satisfied byhydrogen, or from 0 to 3 substituents which may be lower alkyl, moreusually alkyl of from 1 to 3 carbon atoms, amino, and aminoalkyl of from2 to 3 carbon atoms. The total number of carbon atoms of theheterocyclic radical will not exceed 16 and usually will not exceed 8.

Illustrative heterocyclic radicals provided for by the above formulaeare morpholine and alkyl substituted morpholines, piperazines such aspiperazine, 2,6-diamino piperazine, N-2-aminoethyl piperazine, andN,N'-di(2- aminoethyl)piperazine; imidazolines such as imidazoline,N-(Z-aminoethyl imidazoline), and 4-methyl imidazoline; pyridines suchas pyridine, 2 aminopyridine and 2,6- di(tert.-butyl)pyridine; anddiazines and triazines such as 1,3-diaminotriazine, aminomethyl,diazine, etc.

Finally, nitrile substituted olefins and basic nitrogen derivativesthereof may also be used, the nitriles primarily as intermediates. Theseolefins have the following formulae:

'wherein X is alkylene of from 1 to 10 carbon atoms, more usually offrom 2 to 6 carbon atoms, and preferably polymethylene; T and T arehydrocarbon radicals of from 1 to 6 carbon atoms, or hydrogen, moreusually saturated aliphatic hydrocarbons of from 1 to 3 carbon atoms(alkyl); A is oxygen or nitrogen and Z and p are as defined previously.

The polymers of this invention can be prepared in a variety of ways. Apreferred and novel method is to directly incorporate an aminecontaining a-olefin with 2 hydrocarbon olefins into a polymer. This canbe achieved by using an alkyl aluminum or alkyl aluminum halidecatalyst, e.g., alkyl aluminum sesquichloride, dialkyl aluminum chlorideand trialkyl aluminum wherein the alkyl groups are of from 1 to 3 carbonatoms, preferably ethyl, with vanadium oxychloride. (The trialkylaluminum may be used with activated titanium trichloride.)

The ratio of atoms of aluminum to atoms of vanadium is not particularlycritical, there being from 2 to 20 atoms of aluminum per atoms ofvanadium, usually from 2 to 10 atoms of aluminum per atoms of vanadium.Critical to the process is the ratio of amine containing olefin toaluminum. There should be not more than 1 mole of amine or basicnitrogen containing olefin per atom of aluminum in the catalyst andpreferably there should be not more than 1 equivalent of basic nitrogenper atom of aluminum in the catalyst. Usually, there will be from about0.1 to 1 equivalent of basic nitrogen per atom of aluminum in thecatalyst.

The temperature for the reaction will generally be in the range of about10 to 100 C. Depending on the monomers-gases or liquids at roomtemperature-the pressure may vary from atmospheric pressure to 100 psi.

The solvents used will generally be inert hydrocarbons which are liquidsat the temperature of reaction. Illustrative solvents are heptane,octane, benzene, toluene, xylene, etc. The concentrations used willgenerally be about 1 mm. of aluminum in from about 0.10 to 5 liters ofsolvent.

The process is novel and may be used to form copolyberstwo monomers, orhigher order polymers-terpolymers having three monomers. The hydrocarbonmonomers will be a-olefins of from 2 to 6 carbon atoms. With gaseousa-olefins, the olefin is fed into the solvent at a convenient rate,while the liquid a-olefins, all of the olefins may be added initially orduring the course of the polymerization, maintaining a proportionateconcentration in solution of the aminoolefin.

Molecular weight of the polymer may be controlled by conventional means,e.g., hydrogen.

The product is worked up in the normal manner. The polymer is isolatedand then extracted with methanol to remove catalyst residues and dried.Various modifications of this procedure are well known and appear in theliterature.

By means of the above process, terpolymers are obtained which haveexcellent solubility in the hydrocarbon media in which, for the mostpart, they are employed.

Alternatively, a halo substituted olefin may be copolymerized with thedesired hydrocarbon olefins and then the halogen displaced with a basicnitrogen compound. A method for preparing copolymers of hydrocarbonolefins and halohydrocarbon olefins is disclosed in copendingapplication Ser. No. 304,958, filed Aug. 27, 1963. In that application,an organo-aluminum compound is used with either titanium trichloride orvanadium oxychloride and a Lewis base such as a tertiary amine ordialkyl ether.

The displacement reaction with the amines is generally carried out in aninert solvent. Suitable solvents include chlorobenzene, toluene, orhigher boiling aromatic or chloroaromatic solvents, etc. Generally, thetemperature will be in the range of about to 200 C. With volatile aminesor solvents, pressures above atmospheric will be used to maintain thereaction mixture in the liquid state. Otherwise, atmospheric pressureswill sulfice. The amount of amine used will be from about 1 to 10 molesper atom of bromine. The time for the reaction is dependent on the othervariables, generally being in excess of one hour and usually notexceeding 24 hours.

The method of preparing the polymer should provide for its use as alubricating oil additive. Generally, the methods described in thisapplication using Ziegler-type" catalysts are preferred. These catalystsemploy a Group III organo-metallic compound with either a titanium orvanadium halide or oxy compound giving nonstereoregular polymers.

The following examples are offered by way of illustration and not by wayof limitation.

Example I Into a reaction flask was introduced 0.5 g. (-2 mm.) of ethylaluminum sesquichloride, 0.05 g. (-0.6 mm.) of vanadium oxychloride, 300ml. of dry n-heptane and 1.0 millimoles N-( 8-[1-octenyl] triethylenetetramine and the flask flushed with nitrogen. Into the resultingsolution at room temperature was then introduced ethylene at a flow rateof 600 ml. per minute and propylene at a flow rate of 1,400 ml. perminute and the flow maintained for 30 minutes. At the end of this time,the catalyst was quenched with methanol, the precipitated polymer washedtwice with methanolic hydrochloric acid, then with methanol, aqueousammonium hydroxide, followed by methanol and acetone and then vacuumdried at 85 C. The yield was 7.1 g. Analysis: Wt. percent N=0.2S, 0.24;intrinsic viscosity (Tetralin at C.)=0.65 dl./g.

Following the procedure described above for batch preparations and usinga variety of nitrogen substituted olefins and a mole ratio of ethyleneto propylene of 6 to 14 (as in Example I), various products wereprepared which are tabulated in the following table. The ethylene wasintroduced at a rate of 600 ml./min. and the propylene at a rate of1,400 ml./min.

the sample to be tested. The viscosity measurements are determined at210 F. and reported in SUS. The shear test TABLE I Analysis, Millimolesweight. Milli- Time, Temp, Yield, a percent Ex. No. Nitrogen containingmonomer moles EASC l V0013 2 min. grams (dl/g.) N

II. Edimethylamino-octene-I 3.0 3. 4 3.0 30 25 11 1.8 0. 24 III de 3.03. 4 3.0 30 25 12. 1. 9 (I. 26 IV .110... 3. 0 3.4 3. 0 30 3. 7 2. ()50.16 V dc 3.0 3.4 3.0 25 8.1 2.08 0.29 VI N-allylhexaniethyldisilazane2.0 2.0 0.3 30 25 3.1 0.23 VII S-triethyleno tetra-amino octane-l 0. 32.0 0.6 60 25 7. 1 0. 18 VIII 8-(N-(2-aminoethyl)-piperazinesubstituted) octane-1"... 1. 0 2.0 0. 6 30 25 4. 2 4. 41 0.33 IX.S-(diethylene triamino) octane-1 1. 0 2.0 0. 6 30 25 5. 3 0. 34 Scyanooctene-l 1. 0 2 0. 6 30 0 9. 3 1.96 0. 06 Allylcya .nide 1.0 2 0.6 30 256.4 1.67 0.15 S-hexainothylsilazanylo 2. 0 1.0 0.6 30 25 3.6 0.26

l Ethyl aluminum sesquichloride. I Vanadium oxychloride. 3 Intrinsicviscosity.

Polymers having amines directly incorporated were is carried out atabout 77 F. for 20 mins. in a sonic oscilprepared in a continuous manneras follows. lator.

TABLE II Nitrogen M lllimoles Shear loss, containing Time, Temp., Yield,Percent V percent Ex. No millimoles EASC VOCl; min. C. grams N SUS AV so32s 69 10s as 1, 000 0. 13 54. s 4 56 312 61 102 as 1, 000 0. 07 61. 2 556 29s 60 110 as 1, 000 0. 01 so. 9 4

Example XIII The following example demonstrates an alternative route tothe preparation of the compounds of this inven- Into a reaction vesselwas introduced 5 gallons of benzene and 20 g. of1-(2-aminoethyl)-2-(8-[9-decenyl])- irnidazoline and the mixture heatedto 102 F. Solutions were prepared in benzene, one having 25% ethylalumi' num sesquichloride and the other 6.905 weight percent vanadiumoxychloride. A sufficient amount of the ethyl aluminum sesquichloridewas added to the benzene solution to complex the amine containingmonomer and the vessel pressured with propylene. Then, the vanadiumoxychloride solution was added at a rate of 88 g. per hour, the ethylaluminum sesquichloride solution was added at a rate of 125 g. per hourand a :50 mixture of ethylene/ propylene gas was added at a rate so thatover a 1 hour and 14 minute period 1,000 g. of the gas mixture wasadded. During the run, the pressure ranged from about 9.1 to 11.3 p.s.i.The total amount of vanadium oxychloride solution added was 185 g.,while the total amount of ethyl aluminum sesquichloride solution addedwas 335 g. The product was precipitated with a methanolic HCl solutionand twice extracted with acetone. The polymer was then isolated byfiltration and dried. Analysis: Wt. percent N, 0.101; viscosity at 210"F., 94.3 Saybolt Universal Seconds (SUS) (2.8 wt. percent in 130 neutraloil).

Following the procedure described above, a number of polymers wereprepared having differing nitrogen contents and using as the basicnitrogen containing monomer 1-(2-aminoethyl)-2(8-[9-decenyl])imidazoline. However, the results reported are for the polymer prior toextraction.

Also reported in the table are the viscosities at 210 F. in SUS (2.8 wt.percent in 130 neutral oil) and the shear. An extremely severe sheartest is used: the degree of oscillation necessary to reduce acommercially available polyisobutylene thickener (Paratone N supplied byEnjay Chemical Co.) by 29% (Vis v /Vis -V um x 100) is determined andthe same severity used with tion. In this example, a terpolymer ofethylene, propylene and 8-bromooctene-1 is first prepared, and then thebromine displaced with various amines.

Example XVII (A) Into a reaction flask was introduced 300 ml. of dryn-heptane, 0.83 g. of ethyl aluminum sesquichloride, 0.24 g. ofpyridine, 1.0 g. of 8-bromooctene-l and 0.52 g. of vanadium oxychlorideand the flask flushed with nitrogen. Into the resulting solution at roomtemperature was then introduced ethylene at a flow rate of 600 ml. perminute, propylene at a flow rate of 1,400 ml. per minute, hydrogen at afiow rate of 13 ml. per minute and the flow maintained for 30 minutes.At the end of this time the catalyst was quenched with isopropanolichydrochloric acid, and the polymer precipitated into methanol, washedwith methanolic hydrochloric acid, methanol, followed by acetone anddried in a vacuum oven at C. for 12 hours. The yield was 11.8 g.Analysis: Wt. percent Br=2.17; intrinsic viscosity (Tetralin at 135C.):0.9l5 dl./g.

(B) Into a flask was introduced 150 g. of polymer (prepared as describedabove) containing 0.81 weight percent bromine dissolved in benzene, 1.5g. of 50 weight percent aqueous sodium hydroxide and 24.3 g. ofZ-aminocthylpiperazine. The temperature was raised to C. whiledistilling olf the benzene and adding chlorobenzene. The reaction wasmaintained at 120 C. for 20 hours. The polymer was then precipitatedinto methanol, washed with methanol and acetone and dried. The yield wasg. Analysis: Wt. percent N=0.33, 0.31; wt. percent Br: 0.085; viscosityindex=133.

Following the above procedure using polymers having varying amounts ofbromine, various amines were used to substitute the bromines to providea variety of polymers within the purview of this invention.

TABLE 111 Weight percent Br Weight Temp., Time, Ex. No. Amine BeforeAfter percerrrrt Pressure 0. hr.

XVIII Dimethyl amine 2.8 XIX Di-u-gropyl amine 1.8 XX Di(2-ydroxyethyl)amtne. 2.6 XXL.v Trlethylene tetrumlne- 2. 6 1. XXIL. -doXXIII. do XXIV. N-[2nmlnoethyl)piperazln XXV" Triethylene tetramme. 0.66

XXVII- Morphollne XXVIIL. Diethylene triamine XXIX ..do

The polymers of Examples XXVII and XXVIII were tested for shearstability according to the test previously described. The following arethe results.

Shear loss,

Example: percent AV XXVII 7 XXVIII 2 The compounds of this invention canbe used with various base oils which find use as lubricating oils, suchas the naturally occurring naphthenic base, paraffin base, asphalticbase and mixed base petroleum lubricating oils. Synthetic lubricantsinclude alkylene polymers, such as polymers of propylene, butylene,etc.; alkylene oxide type polymers and derivatives, dicarboxylic acidesters, such as octyl adipate, isooctyl azelate, hexyl alkenylsuccinate,etc.; and inorganic esters such as phosphates and silicates.

The above base oils may be used individually or in combination whenevermiscible or made so by the use of mutual solvents.

The compositions of this invention can be used in oils of lubricatingviscosity in amounts of from about 0.1 to 80 weight percent, dependingon the use of the composition. When concentrates are to be used, priorto use in the engine, the amount will vary from about 10 to 80 weightpercent. When the oil is to be used in an engine, usually the amount ofthe additive will be in the range of about 0.1 to 10 weight percent,more usually 0.25 to 5 weight percent. Concentrates are possible becauseof the excellent compatibility of the compositions of this inventionwith the various base oils.

In order to demonstrate the use of the compositions of this invention asviscosity index improvers, a number of the polymers were tested in a 130neutral oil, for the most part at 2.8 weight percent, the Sayboltviscosity being determined both at 100 F. and 210 F. and the viscosityindex determined therefrom. The following table indicates the results.

TABLE IV Polymer Ex. No.

2.5 weight percent in 130 neutral oil.

It is evident from the above results, that the polymers of thisinvention enhance the viscosity index of lubricating oils.

In order to demonstrate the effectiveness of the compositions of thisinvention as detergents in engines, a number of the compositions weretested according to a modified standard FL-Z test procedure as describedin the June 21, 1948 report of the Coordinating Research Council. Astandard procedure requires the maintenance of a jacket temperature of95 F. and a crankcase oil temperature of 155 F. at 2,500 rpm. and 45brake test, the engine is dismantled and the amount of sludge (rating of0 to 50, no sludge being 50) and varnish (rated in the same way) isdetermined. Also determined is ring clogging reported as percent ringclogging.

The above test is modified by carrying out the test while periodicallyraising the oil sump temperature from 165 to 205 F. and the water jackettemperature from to 170 F. The oil sample used is a Mid-Continent baseoil SAE 30 containing 2.5 weight percent of the candidate detergent and15 mm./kg. of zinc 0,0-di(alkyl) phosphorodithioate (alkyl of from 4 to6 carbon atoms). The following table indicates the results obtained.

TABLE V Total Total Percent ring varnish sludge clogging It is evidentfrom the above results that the compositions of this invention provideexcellent varnish and sludge control under the severe conditions of thetest, which approximate the conditions of normal everyday automobiledriving.

A number of the compositions of this invention were compounded inlubricating oils using the usual formulation, except that thecompositions of the invention replaced the usual detergent. Thecompositions showed excellent detergency and maintained theirperformance over long periods of time.

To further demonstrate the effectiveness of the compositions of thisinvention as dispersants, a bench test was used described by C. B.Biswell et al., Ind. Eng. Chem. 47 1958, 1601 (1955). A solution wasprepared by using 10 g. of a 2.8 weight percent solution of thecandidate dispersant in 130 neutral oil and diluting this with 70 ml. ofpearl oil. To this was added in a Waring Blendor 3 g. of a 20 weightpercent slurry of carbon black in mineral oil. After blending for 3minutes, the mixture was immediately poured into a 50 ml. stopperedgraduate.

An inspection was made by periodically noting the level to which thecarbon black had settled using a bright lamp. The results are reportedas percent; is no discernible settling.

Example XXV Example XXVII 98%, 21 days 90%, 21 days The testdemonstrates the excellent detersive capability of the compounds of thisinvention in retaining carbon black suspended in a hydrocarbon medium.

Of particular value are the polymers having from 0.06 to 1.0 weightpercent nitrogen, wherein the nitrogen is obtained from alkylenepolyamines (including piperazines).

A preferred aspect of this invention employs zinc 0,0 dihydrocarbylphosphorodithioates in the engine oil with the detergents of thisinvention. The hydrocarbyl groups are of from 4 to 36 carbon atoms andabout 1 to 50 mm./kg. of the dithiophosphate is used. Preferably, thehydrocarbyl groups are alkyl or alkaryl.

It is evident that the compounds of this invention not only provideviscosity index improvement in lubricating oils but also neutralizeacids formed from the oxidation of the lubricating oil and maintainproducts dispersed in the oil which otherwise form sludge and varnishdeposits and clog rings.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed, in the light of the foregoingdisclosure and discussion, without departing from the spirit or scope ofthe disclosure or from the scope of the following claims.

I claim:

1. A hydrocarbonaceous oil soluble random terpolymer having an intrinsicviscosity of from about 0.2 to 1.5 dl./ g. and from about 0.05 to 2weight percent basic nitrogen, wherein two of the olefins of saidterpolymer are aliphatic l-olefins of from 2 to 6 carbon atoms which areeach individually present in at least 30 mole percent, the total molepercent of said 2 olefins is in the range of 95 to 99.95, and the thirdolefin is a basic nitrogen containing olefin which is present in formabout 0.05 to 5 mole percent and is of the formula:

X is an alkylene group of from 1 to carbon atoms;

Y is a basic nitrogen containing radical, wherein the basic nitrogen isat least beta to the olefinic group, of from 0 to 16 carbon atoms, 1 to6 basic nitrogen atoms, 0 to 2 silicon atoms, said silicon atoms beingcombined with amino groups to form silazane groups, and from 0 to 2oxygen atoms, said oxygen atoms being present as hydroxyl or etherealfunctional groups, and

wherein said terpolymer is prepared by polymerizing said olefins at atemperature in the range of 10 to 100 C. in an inert hydrocarbon diluentin the presence of a complex catalyst comprising vanadium oxychlorideand an alkyl aluminum compound selected from the group consisting ofalkyl aluminum sesquichloride, dialkyl aluminum chloride and trialkylaluminum, wherein the alkyl groups are of from 1 to 3 carbon atoms,

wherein the ratio of aluminum to vanadium is in the range of 2 to 20atoms of aluminum per atom of vanadium and there being from 0.1 to 1mole of said amino containing olefin per atom of aluminum in thecatalyst,

with the proviso that the hydrocarbon olefins are maintained in solutionduring the polymerization at a substantially constant mole ratio.

2. A terpolymer according to claim 1, wherein the mole percent of saidbasic nitrogen containing olefin is in the range of 0.1 to 3.

3. A terpolymer according to claim 1, wherein Y is:

and wherein T and T are the same or dilferent and are hydrogen,hydrocarbon radicals of from 1 to 12 carbon atoms, hydroxy or alkoxyhydrocarbon radicals of from 2 to 10 carbon atoms or trialkyl silylradicals of from 3 to 12 carbon atoms.

4. A terpolymer according to claim 1, wherein Y is:

{NH( Z 1 131-111,

and wherein Z is alkylene of from 2 to 6 carbon atoms, there being atleast 2 carbon atoms between the nitrogen atoms, and p is an integerfrom 1 to 5.

5. A terpolymer according to claim 1, wherein Y is wherein N and C havetheir ordinary meaning of nitrogen and carbon; A and D may be the sameor diflerent and are nitrogen or oxygen; a, c and e are integers of from0 to 3; b and d are integers of from 0 to 1; the sum of a, b, c, d and eis in the range of 4 to 5, the total number of carbon atoms being notgreater than 16, there being from 0 to 3 alternating double bonds in thering, and the remaining unsatisfied valences of A and D, when they arenitrogen, and the annular carbon atoms are satisfied by a member of thegroup consisting of hydrogen, lower alkyl and aminoalkyl of from 2 to 3carbon atoms.

6. A terpolymer according to claim 1, wherein Y is cyano.

7. A terpolymer according to claim 1, wherein X is polymethylene of from2 to 6 carbon atoms.

8. A terpolymer according to claim 1, wherein said aluminum alkyl isalkyl aluminum sesquichloride.

9. A terpolymer according to claim 1, wherein said hydrocarbon olefinsare ethylene and propylene.

10. A terpolymer according to claim 9, wherein ethylene is present infrom 45 to 60 mole percent and propylene is present in from 55 to 40mole percent.

11. A lubricating oil composition comprising from 0.1 to weight percentof a hydrocarbonaceous oil soluble random terpolymer having an intrinsicviscosity of from about 0.2 to 1.5 dl./g. and from about 0.05 to 2weight percent basic nitrogen, wherein 2 of the olefins of saidterpolymer are aliphatic l-olefins of from 2 to 6 carbon atoms which areeach individually present in at least 30 mole percent, the total molepercent of said 2 olefins is in the range of to 99.95, and the thirdolefin is a basic nitrogen containing olefin which is present in fromabout 0.05 to 5 mole percent and is of the formula:

wherein X is an alkylene group of from 1 to 10 carbon atoms;

Y is a basic nitrogen containing radical of from 0 to 16 carbon atoms, 1to 6 basic nitrogen atoms, 0 to 2 silicon atoms, said silicon atomsbeing combined with amino groups to form silazane groups, and from 0 to2 oxygen atoms, said oxygen atoms being present as hydroxyl or etherealfunctional groups.

12. A lubricating oil composition according to claim 11 wherein saidaliphatic olefins are ethylene and propylene.

13. A lubricating oil composition according to claim 12, wherein saidethylene is present in from 45 to 60 mole percent and propylene ispresent in from 55 to 40 mole percent.

14. A lubricating oil composition according to claim 11, wherein Y is:

and wherein T and T are the same or diiferent and are hydrogen,hydrocarbon radicals of from 1 to 12 carbon atoms, hydroxy or alkoxyhydrocarbon radicals of from 2 to 10 carbon atoms or trialkyl silylradicals of from 3 to 12 carbon atoms.

15. A lubricating oil composition according to claim 11, wherein Y is ofthe formula:

{N11 ll l}: u and wherein Z is alkylene of from 2 to 6 carbon atoms,there being at least 2 carbon atoms between the nitrogen atoms, and p isan integer from 1 to 5.

16. A lubricating oil composition according to claim 11, wherein Y is ofthe formula:

ii u

-(.3QD4 wherein N and C have their ordinary meaning of nitrogen andcarbon; A and D may be the same or different and are nitrogen or oxygen;a, c and e are integers of from to 3; b and d are integers of from 0 to1, the sum of a, b, c, d and e is in the range of 4 to 5, the totalnumber of carbon atoms being not greater than 16, there being ReferencesCited UNITED STATES PATENTS 2,749,312 6/1956 Hollyday 252 2,838,4566/1958 Banes et al. 25250 3,000,822 9/1961 Higgins et al.

3,092,563 6/1963 Agius et al 252 50- XR 3,125,462 3/1964 Rachinsky26080.73 XR 3,293,326 12/1966 Jezl et a1 26080.73 XR 3,308,108 3/1967Felclhofi et al. 2603S.1

PATRICK P. GARVIN, Primary Examiner.

US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,445,387 May 20, 1969 Thomas V. Liston It is certified that errorappears in the above identified patent and that said Letters Patent arehereby corrected as shown below:

Column 2, line 43, "is intended which" should read is intended nitrogenwhich Column 3, line 51, "the containing" should read the aminecontaining Column 5, line 31,

L "2 {minopyridine" should read Z-aminopyridine line 45 f"hy rocarbons"should read hydrocarbon lines 60 and 61, "'atoms", each occurrence,should read atom Column 6,

line 10, "of the olefins" should read of the olefin line 33, "amines"should read amine Column 8, TABLE I, the last column should appear asshgwn below:

Analysis Wt. N

OCDOQQOOOQOCD Column 7, TABLE II, the first heading following Ex. No.,should appear as shown below:

Nitrogen Containing Monomer Millimoles Signed and sealed this 28th dayof April 1970.

( E Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting OfficerCommissioner of Patents

